Sulphones and method of preparing same



Patented Nov. 20, 1945 SULPHONES AND METHOD OF PREPARING SAME Louis L. Bambas, Grosse Pointe Woods, Mich, as-

signor to Parke, Davis & Company, Detroit, Mich, a corporation of Michigan No Drawing. Original application December 13,

1941, Serial No. 422,904. Divided and this application June 13, 1944, Serial No. 540,139

6 Claims. (Cl. 260239.6)

The invention relates to sulphones and their preparation.

This application is a division of my copending application, Serial No. 422,904, filed December 13, 1941.

This divisional application relates more particularly to sulphones having the general formula Z SOA Where Z and Z are each a member of the class consisting of NO2, NH2 and groups hydrolyzable to -NH2.

The new sulphones may be prepared from a thiophene compound of the formula H-C---CH II lg Halogen-C N O 3 by a condensation with a sulphinic acid or salt thereof, of the formula where M is H or a metal. Thus M may be silver, lead sodium, and the like. The condensation is readily effected, preferably by heating in a solvent inert to the reactants. The resulting sulphone of formula may be condensed with a mercaptan, or salt thereof, of the formula This condensation is likewise best conducted by heating the reactants in an inert solvent. The resulting sulphide can be converted into the corresponding sulphone of formula by oxidation, e. g., with hydrogen peroxide'or with chromic acid. Since free amino groups are readily attacked by these reagents, the sulphide must be acylated prior to oxidation if Z is NH2 My invention may be further illustrated by the following example.

Example (a) 2-iodo-5-nitrothiophene, M. P. '75-'78 C. is prepared by the nitration of 2-iodothiophene according to the directions of Rinkes, Rec. Trav. Chim. 53, 648 (1934).

(b) The sodium salt of p-acetylaminobenzenesulphinic acid is prepared by dissolving 30 grams of the acid in cc. of Water containing sufiicient sodium hydroxide to neutralize the acid. Then 30 grams of 2-iodo-5-nitrothiophene in cc. of alcohol is added, and the mixture is refluxed for about ninety minutes. The crystalline precipitate of p-acetylaminophenyl-5' nitro 2- thienyl sulphone is collected and recrystallized from isopropyl alcohol, M. P. 184-187 C.

(c) The above acetyl derivative is refluxed for fifteen minutes in alcoholic hydrochloric acid. Then an equal volume of water is added, and the mixture is made alkaline to litmus; the precipitate is collected and crystallized from isopropyl alcohol to give p-aminophenyl-5'-nitro- 2'-thienyl sulphone, M. P. 159-162 C.

What I claim as my invention is: 1. A sulphone having the formula where Z and Z are each a member of the class consisting of -NO2, NH:; and groups hydrolyzable to -NH2.

2. p-acetylaminophenyl 5' nitro 2'-thienyl sulphone.

3. p-aminophenyl 5 nitro 2' thienyl sulphone.

4. Process for preparing a sulphone of the formula where Z and Z ar each a member of the class consisting of NO2, NH2 and roups hydrolyzable to NH2 which comprises reducing a sulphone of the formula 5. Process for preparing a sulphone of the formula where Z and Z are each a. member of the class consisting of -NO2, NH2 and groups hydrolyzable to NH2 which comprises condensing a compound of the formula.

H-(I?(I'IJH Halogen-C C-NO:

with a compound of the formula z sor-M where M is a member of the class consisting of H and a metal.

6. Process for preparing a sulphone of the formula II C-NO:

with a compound of the formula where M is a, member of the class consisting of -H and a, metal, and reducing the compound thus obtained to convert an NO2 group to an NH group.

II halogen-0 LOUIS L. BAIVIBAS. 

